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Homogeneous Catalysis with Earth-Abundant Metal Complexes

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 13816

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Special Issue Editor

Dr. Dmitry A. Valyaev

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Guest Editor

Laboratoire de Chimie de Coordination du CNRS, Toulouse, France
Interests: transition metal organometallic chemistry; metal-mediated synthesis; homogeneous catalysis; organophosphorus chemistry; N-heterocyclic carbenes; electrochemistry; non-covalent interactions

Special Issue Information

Dear Colleagues,

Replacement of noble transition metal complexes in homogeneous catalysis with more abundant, cheaper, and often less toxic alternatives based on Earth-abundant metals constitutes an important aspect in the development of sustainable fine chemical industry. Since the beginning of the 21st century, this research area has become providing a plethora of highly efficient catalytic systems, which are competitive or sometimes even superior to traditional noble metal catalysts.

This Special Issue focuses on the application of both well-defined species and generated in situ catalytic systems as well as on the experimental and theoretical studies of catalytic reaction mechanisms. In addition to first row transition metal catalysts, the scope of the issue also concerns other (relatively) abundant main group (Mg, Ca, Ba, Al, Ga) and heavier transition metal (Zr, Mo, W) complexes.

The possible contributions include communications, research papers, and short reviews.

Dr. Dmitry A. Valyaev
Guest Editor

Manuscript Submission Information

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Keywords

Homogeneous catalysis
Earth-abundant metals
3d transition metal catalysts
Alkaline earth metal catalysts
Mechanistic studies
DFT calculations

Published Papers (4 papers)

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Research

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25 pages, 4270 KiB

Open AccessArticle

Investigations on the Ethylene Polymerization with Bisarylimine Pyridine Iron (BIP) Catalysts

by Elsa M. Schoeneberger and Gerrit A. Luinstra

Catalysts 2021, 11(3), 407; https://doi.org/10.3390/catal11030407 - 23 Mar 2021

Cited by 6 | Viewed by 3291

Abstract

The kinetics and terminations of ethylene polymerization, mediated by five bisarylimine pyridine (BIP) iron dichloride precatalysts, and activated by large amounts of methyl aluminoxane (MAO) was studied. Narrow distributed paraffins from initially formed aluminum polymeryls and broader distributed 1-polyolefins and (bimodal) mixtures, thereof, were obtained after acidic workup. The main pathway of olefin formation is beta-hydrogen transfer to ethylene. The rate of polymerization in the initial phase is inversely proportional to the co-catalyst concentration for all pre-catalysts; a first-order dependence was found on ethylene and catalyst concentrations. The inhibition by aluminum alkyls is released to some extent in a second phase, which arises after the original methyl groups are transformed into n-alkyl entities and the aluminum polymeryls partly precipitate in the toluene medium. The catalysis is interpretable in a mechanism, wherein, the relative rate of chain shuttling, beta-hydrogen transfer and insertion of ethylene are determining the outcome. Beta-hydrogen transfer enables catalyst mobility, which leads to a (degenerate) chain growth of already precipitated aluminum alkyls. Stronger Lewis acidic centers of the single site catalysts, and those with smaller ligands, are more prone to yield 1-olefins and to undergo a faster reversible alkyl exchange between aluminum and iron. Full article

(This article belongs to the Special Issue Homogeneous Catalysis with Earth-Abundant Metal Complexes)

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11 pages, 3120 KiB

Open AccessCommunication

Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand

by Tat’yana F. Savel’yeva, Olga V. Khromova, Vladimir A. Larionov, Alexander F. Smol’yakov, Ivan V. Fedyanin, Yuri N. Belokon and Victor I. Maleev

Catalysts 2021, 11(2), 152; https://doi.org/10.3390/catal11020152 - 21 Jan 2021

Cited by 14 | Viewed by 2693

Abstract

Chiral metal-templated complexes are attractive catalysts for organic synthetic transformations. Herein, we introduce a novel chiral cobalt(III)-templated complex based on chiral trans-3,4-diamino-1-benzylpyrrolidine and 3,5-di-tert-butyl-salicylaldehyde which features both hydrogen bond donor and Brønsted base functionalities. The obtained complexes were fully characterized by ¹H, ¹³C NMR, IR-, UV-vis, CD-spectroscopy and by a single X-ray diffraction analysis. It was shown that chlorine anion is connected with amino groups of the complex via a hydrogen bonding. DFT calculations of charges and molecular electrostatic potential of the cobalt(III) complex showed that the basicity of the complex is certainly diminished as compared with the routine tertiary amines but the acidity of the conjugated acid of the complex should be increased. Thus, the catalytic potential of the complex may be much greater as a chiral acid than a chiral base. We believe that this work opens a new way in chiral bifunctional catalyst design. Full article

(This article belongs to the Special Issue Homogeneous Catalysis with Earth-Abundant Metal Complexes)

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16 pages, 3223 KiB

Open AccessArticle

Catalytic Systems Based on Cp₂ZrX₂ (X = Cl, H), Organoaluminum Compounds and Perfluorophenylboranes: Role of Zr,Zr- and Zr,Al-Hydride Intermediates in Alkene Dimerization and Oligomerization

by Lyudmila V. Parfenova, Pavel V. Kovyazin, Almira Kh. Bikmeeva and Eldar R. Palatov

Catalysts 2021, 11(1), 39; https://doi.org/10.3390/catal11010039 - 31 Dec 2020

Cited by 9 | Viewed by 2211

Abstract

The activity and chemoselectivity of the Cp₂ZrCl₂-XAlBuⁱ₂ (X = H, Buⁱ) and [Cp₂ZrH₂]₂-ClAlEt₂ catalytic systems activated by (Ph₃C)[B(C₆F₅)₄] or B(C [...] Read more.

The activity and chemoselectivity of the Cp₂ZrCl₂-XAlBuⁱ₂ (X = H, Buⁱ) and [Cp₂ZrH₂]₂-ClAlEt₂ catalytic systems activated by (Ph₃C)[B(C₆F₅)₄] or B(C₆F₅)₃ were studied in reactions with 1-hexene. The activation of the systems by B(C₆F₅)₃ resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp₂ZrH₂∙Cp₂ZrHCl∙ClAlR₂]∙yR_nAl(C₆F₅)_3−n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers. Full article

(This article belongs to the Special Issue Homogeneous Catalysis with Earth-Abundant Metal Complexes)

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Review

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36 pages, 5213 KiB

Open AccessFeature PaperReview

Earth-Abundant 3d Transition Metal Catalysts for Hydroalkoxylation and Hydroamination of Unactivated Alkenes

by Lou Rocard, Donghuang Chen, Adrien Stadler, Hailong Zhang, Richard Gil, Sophie Bezzenine and Jerome Hannedouche

Catalysts 2021, 11(6), 674; https://doi.org/10.3390/catal11060674 - 25 May 2021

Cited by 22 | Viewed by 4945

Abstract

This review summarizes the most noteworthy achievements in the field of C–O and C–N bond formation by hydroalkoxylation and hydroamination reactions on unactivated alkenes (including 1,2- and 1,3-dienes) promoted by earth-abundant 3d transition metal catalysts based on manganese, iron, cobalt, nickel, copper and [...] Read more.

(This article belongs to the Special Issue Homogeneous Catalysis with Earth-Abundant Metal Complexes)

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